text:
I would trade the best as I can, really struggling to get this hidden ability spending hours just to get it.
What the hell is Nuzlocke?
I would trade the best as I can, really struggling to get this hidden ability spending hours just to get it.
Use the Trade Forum if you're looking for a Pokemon.
Hey I haven't been on this website in a while and I don't remember if this is the place to ask for a trade (didn't see any other area that might be a trade forum). Anyway, I need a ditto with a perfect (31) IV in attack, if anyone could oblige I'd be thankful! I can give a ditto with any other perfect IV stat. Thanks!
This is the trade forum:
This is the ditto thread:
Finally opened my trade shop and breeding grounds. Feel free to check it out for IV pokemon and shinies.
IGN: Serpent (Pokemon Y)
IGN: Wayne (Pokemon Omega Ruby)
And this thread is now closed.
Competitive/IGRMT Mod, one of the writers for the PotW, and (apparently) best regular mod of 2014. Also now available in orange!
I make no claim of being perfect or always right. Take everything I say with a grain of salt.
I would like to hear about ideas for event pokemon! The two I have are both for Mega Charizard X and Y. Mega Charizard X, being a physical fighter, would have the move Sacred Fire, giving him a unique and cool physical STAB. The other, Mega Charizard Y, would know the move Aero Blast, capitalizing on the high special stat and STAB. I think both would be quite cool, and if such an event happened, you would have to choose just one.
Friend Code: 3712-0195-9885
Friend Safari: Ice - Snover, Beartic, Piloswine
So the title really explains the topic. What do want in the next game?
I know two things I really want are
1) More post game material like the Booker detective agency
2) Gym Customization after league complication. Like, you make your own gym your friends can visit, and you can invite the NPC's you met on the road in to act as those pesky trainers that interrupt you while you try to solve that stupid puzzle. They then fight your avatar as a gym leader.
Bonus: You get to design a simple badge like in animal crossing.
1) It's the Looker detective agency
2) Isn't that just Super Secret Bases?
3) This thread will be locked soon as we don't allow future game speculation here.
Current Hunts
200 Icebirds
Route 25 - Phase 3 (pending)
Omega Ruby Current MM
110 Eggs COMPLETE!!!
I think an Event Jigglypuff with Metronome would be neat. I've always believed that Jigglypuff should have been able to use the move since it is basically the counterpart to Clefairy. Also a Glameow with Pay Day and a Meowth with Happy Hour.
"Hey! Don't pawn your trash on me!" Watchy Watchog
More type combinations and Pokemon. Shame Gen. 6 had a lack of unique type combinations and new Pokemon. I'd like to see a Poison/Steel, Dark/Fairy, Fire/Ice, Bug/Psychic, Bug/Dragon, Electric/Fighting, Electric/Dark, Ground/Fairy, etc.
I think a feature where you can replace HMs in the move poll after defeating the Champion could be nice as well.
I'd like to see moves like Bubblebeam and Dragonbreath to return as a TM or Move Tutor move.
A feature where you can customize your own clothes.
I'd like to see Little Cup battles
My current shinies!
Gifts: SR
Trade: Dex-Nav:
X/Y FS: Chain Fishing:
FC for X: 2809-7726-5588
Type: Poison- Cascoon, Garbador and Drapion
Made by Sworn_Metalhead
Hi guys not sure if this is the right place but I didn't know where else to post it so... Anyway I've been having fun creating pokemon cards using the mtg mechanics and would love to see what you think.
Here's a look of what I have done so far.
Spoiler:- Set (10/???):
This belongs in the Fan Art section.
Made by Sworn_Metalhead
So I started playing a new beta yesterday, for Valhalla Lost. It's pretty cool so far, especially the artwork. I want to try the PvP, but it's still really new so I haven't had much chance. Has anyone tried it yet?
Sorry, but discussion of fangames that infringe on Pokemon copyright isn't allowed anywhere on the forums. http://www.serebiiforums.com/showthr...i-Forums-Rules
Going to have to close as a result, I'm afraid. Please check the rules in future, and PM if you have any questions!15. Don't discuss fan-games.
Don't discuss or provide links to fan made pokemon games. Such games are illegal by default, and as such are not permitted here at all.
A parody of the Pokemon Colosseum game, full of pastries and Miror B.
Completed. Four times winner of Best Comedy/Funniest Fic.
The BBS Fandex! Browse/upload Pokemon Fanworks!
Tied to this Pokemon Magazine! Looking for contributors!
Why should you? Well, Wynaut?
Current Article: Pokemon Go! The new AR mobile phone game just announced!
Previous Article: Game Plot Analysis - The Hoenn Games! Better or worse?
Avatar: minty-fivestar on DA, edited background/cropping. Fic banner: cieux.


text:
WASHINGTON – The campus police at the University of Maryland have issued an alert after a robbery Tuesday night.
The incident occurred around 10:30 p.m. At Princeton and Hartwick roads in College Park, three blocks south of Fraternity Row. Police are searching for the suspects who were driving a silver Lexus with Maryland plates: 5AP0666.
Students are urged to be careful and lock their doors.
Follow WTOP on Twitter.
(Copyright 2012 by WTOP. All Rights Reserved.)
In Maryland, all sorts of marine life is living among more than 100 sunken ships.

subset: commoncrawl


text:
Finance Guru Launches Her Own Debit Card To Help America Stay Debt Free
Suze Orman uses her credibility to create a self-branded MasterCard that is completely secure and will never let you overspend.
Suze Orman has been a financial adviser on CNBC's popular TV program, The Suze Orman Show. Her positive reputation for giving practical and realistic financial advice to everyday people has led her to launch her own prepaid credit card that will help consumers to stay debt free. The Approved Card is essentially a debit MasterCard and is accepted like a credit card in retails, online shops, and stores. However, the big difference between the prepaid card and a credit card is that you will need to top it up with your own money before you can use it.
One unique feature of the Approved Card is that it gives consumers unlimited free access to their credit report and credit score from TransUnion. On the Approved Card's website, Orman lists that the card is safer than cash, debt-free and FDIC-insured as some of the reasons why the card is "the smart choice for you." Orman also added in a statement that:
This is my answer for all those who are looking for a better way to bank, use plastic and feel secure knowing that their interests are being put before fees and profit motives.
Purchasing the card will cost $3 and there's a monthly fee of $3. In addition, there are also additional ATM transaction costs.
- Share
- | Today
PSFK Labs Presents
The Future of Connected Life
The New Consumer and Their Journey to Effectiveness, Balance & Personal Growth


text:
Math doesn't suck, you do.
Math doesn't suck, you do.
Math doesn't suck, you do.
Blue Caves - Zakynthos Island, Greece
Kids write the darndest things when they're failing exams. (Round 2: http://bit.ly/rWGYuB)
The document has moved .
This is a pretty enlightening series of photos showing what happens to an elephant after all of the elephant hunting is over. Nothing is wasted.
Your focus is getting into medical school, but what will you experience once you get there? Dr. Lisabetta Divita, a recent medical school graduate, describes life as a medical student.
Explore thousands of free applications across science, mathematics, engineering, technology, business, art, finance, social sciences, and more.
picsthatdontsuck.com: a data base of hand picked lolin' images! poke dem pics! ; )
www.owned.lv - Daily updated funny pictures and videos. Huge collection of pictures and videos from insane internet. Get your owned today !
Captivity and Extinction - Bear in Mind: The California Grizzly at The Bancroft Library
Chocolate is as good for you as exercise, research suggests.
Includes to locate structures in images.
The waitress asks them for their orders.
SARAH: Daddy, were you in the shower?
Self-Improvement Resource
A locked computer can result in dead-end frustration, potentially costing hundreds of dollars in repair bills. Unlock your computer without the aid of a password-reset disk by accessing the default Administrator account from Safe Mode and unlocking y...
There are so many things out there that we deal with or see everyday, but have no idea what they are called. This is a list of 25 ridiculous real names for 25 everyday items.
Video Lectures, Video Courses, Science Animations, Lecture Notes, Online Test, Lecture Presentations. .
images - Jellyfish, Animal photos, animal pictures. The most beautiful and unique images of nature. Nature photography - pictures of animals, pictures of birds, pictures of butterflies, macro photography of insects, plant photos, pictures of mushroom...
Marine scientists studying sharks in South Africa got closer to their subject than they expected -- when a great white jumped out of the sea and into their boat, according to reports Tuesday.
You are what you eat, but what exactly are you eating? Mealographer s goal is to make it as easy as possible to track what you eat, set simple goals, and see reports on your progress.
Look, if you dig deep enough everything is an amazing coincidence. But even cynics like us have to admit these are downright freaky.
An anti-cancer compound found in broccoli and cabbage works by lowering the activity of an enzyme associated with rapidly advancing breast cancer, according to a University of California, Berkeley, study appearing this week in the online early editio...
Olympic National Park in Washington offers a bit of everything for nature lovers, hikers and adventurers like Pacific Ocean beaches, rain forest valleys, glacier-capped peaks and a dazzling diversity of plants and animals. 95% of this park is still w...
was a game played by and on 21 June 1851 in London, during a break of the . The very bold made by Anderssen to finally secure victory have made it one of the most famous chess games of all time. Anderssen gave up both and a bishop, then his , h...
Think I may give this a go!
is a with a that, when eaten, causes foods (such as and ) subsequently consumed to taste . This effect is due to , which is used commercially as a . for this species and its berry include , , ,, , and in West Africa where the species originates ...
Ghostbusters Jesus
Today in psychology class, I asked my teacher if he was aware that diarrhea was hereditary. He immediately replied "No, it isn't," and proceeded to explain why. I interrupted him with "Sure it is, it runs in the jeans." He was so excited with this re...
Hunter S. Thompson, John Cusack and Johnny Depp riding around with a blow-up doll, date unknown.
Mount Roraima is the highest of the Pakaraima mountain chain in South America. The 31 square kilometer summit area of Mount Roraima is defined by 400 meter tall cliffs on all sides and includes the borders of Brazil, Venezuela, and Guyana. The ...
This is Harry's weather forecasting stone.And below [if i configured adsense correctly] are some ads. You, people, take away a lot of bits and bytes. If ads don't show, and you have some spare virtual money, consider donating it to me. I'll pay for s...
Late last summer, I made some buffalo chicken burgers that rocked the house. They were so delicious that even I, who doesn't need chicken to survive, loved them. And Mr. How Sweet, who absolutelynomatterwhat needs chicken to survive (fact), who calls...
A lady about 8 months pregnant got on a bus.She noticed the man opposite her was smiling at her. She immediately moved to another seat.This time the smile turned into a grin, so she moved again. The man seemed more amused. When on the fourth move,...
Jenny Burrows, art director, advertising, portfolio, book, pdf, work, burrows, jenny, creative
ThermoDex contains records for selected printed and web-based compilations of thermochemical and thermophysical data for chemical compounds and other substances. You can select one or more compound types and link them to one or more property terms, a...
Oakdale, CA: Scientists at Montsaint Genie Tech Inc. announced today that they have successfully transferred the gene segment that produces the psychotropic chemical THC in ca
Hulking Biceps: Lou Ferrigno Arm Workout
For all you guys out there who just can't figure it out, here it is:
are a series of organic molecules whose appear human. et al. () designed and synthesized these compounds in 2003 as a part of a sequence of for young students. The compounds consist of two rings connected via a few carbon atoms as the body, four ...
http://www.bbc.co.uk/bang Follow Bang on Twitter @bbcbang and #bbcbang. Jem Stansfield travels to the Solar Furnace Research Facility in Southern France. He ...
These cookies are every bit as delicious as they look.You may have noticed that I have been in a s'mores kick lately. First with the then with these cookies. I also plan to make additional s'mores themed treats this weekend. I saw a version of s'...
Perfecting health, fitness, and wellbeing
Blogiversity.org: authentic, unique and off the beaten path. News, forums, cartoons & comment from Blogiversity.org; politics, finance, music, editorials, how to, tech reviews, economics, photos, video, privacy, science & entertainment.
Jamaican burgers are spicy vegetarian burgers that are very tasty. They are my favorite to make, and my friends love them!
Below is a list of the bold-faced terms from the Conjoint 401 lab manual. They have been rearranged according to what can be seen in different views of the skull. The links take you to a skull tutorial developed by J. Crimando at Gateway Community Co...
I love being creative - and that state of flow when you are consumed with the project. So, I made a necklace to commemorate it. The charms
Neil degrasse Tyson: Alien vs. Human Intelligence.
fun facts to blow your mind, inspirational quotes, and a complete list of all the worlds phobias.
Quick wine & food pairings chart gives you at a glance suggestions to matching your favorite foods to complementary wines. Use as a resource for your bar's wine rack or for selecting tonight's meal.


text:
Villard Square on Thursday, October 22 and Washington Park on Thursday, October 29.
The Central Library will close early at 3 p.m.
The collection includes indexes to the small selection of employee records that are part of the archives of the Chicago, Milwaukee, St. Paul & Pacific Railway, which designated MPL as…
Do you remember the Live Aid concert, broadcast worldwide on July 13, 1985? What an amazing day!
Book searching coming soon. For now use County Cat
Get the scoop on famous people. Authoritative information from Gale publications on over half a million well-known people from historical times to the present.
Sorry, this event has already happened. Please explore our event calendar for events in the future.


text:
Wharton on Wednesday
5:00 p.m Wed, Jul 17, 2013
Venue: The Mount
2 Plunkett St., Lenox, MA 01240Contact:
0 people saved this
Enjoy summer afternoons on the Terrace while listening to Wharton's short stories read by professional actors. This year's short story series will be book-ended with readings from the novel The Custom of the Country in celebration of its 100th anniversary. Price: Members free; General $5.
Lowell Celebrates Kerouac
Massachusetts is proud of its literary icons – from Henry James and Emily Dickinson to...
Search All Listings Here.


text:
We combine the capabilities of a full-service firm with the responsiveness and flexibility of a specialty engineering practice
River Consulting provides consulting, project management,
multi-discipline engineering, equipment supply, procurement and
construction management services to industrial clients around the globe.
We combine industry insight with technical expertise and proven
methodology to guide our clients through every phase of a project.
River Consulting serves the energy, food, process and industrial
markets. With over three decades and thousands of successfully completed
projects, River Consulting leverages our vast experience to develop
innovative yet practical solutions for our clients most demanding
business challenges.
The Red Bluff natural gas processing plant is a 200 MMSCFD greenfield project designed to produce purified NGL's and natural gas for the petrochemical and utility industries. The Houston Interests companies, River Consulting, Devco and S&R Technical Services, partnered with ISTI Plant Services to provide program management, balance of plant (BOP) engineering, process and systems integration, and procurement support for the construction of the facility.
COLUMBUS, Ohio – River Consulting claimed two spots in the 2015 Top 500 Design Firm Sourcebook by Engineering News-Record (ENR). River Consulting took the 25th spot for the "Refineries and Petrochemical Plants" category and the 42nd spot in the "Industrial Process" category in the recent Engineering News-Record.
Read More »
COLUMBUS, Ohio – River Consulting recently supported a candidate though the Ohio Export Internship Program in collaboration with Youngstown State University and The Ohio State University. The program provides opportunities for motivated, export-focused students, and companies looking to improve their current export initiatives to collaborate.
Read More »


text:
Fair Lawn, NJUSA
Hometown: Fair Lawn
March 24, 2010
I work bankers hours so during the week I sleep usually midnight to 6. But over the weekend I can be flexible.
During the week I like to be asleep by 1 the latest. The weekends I can do whatever.
somewhere where intermediate and advanced meet. Intervanced!
yes and yes
Yes I have. I love capturing motion like a car driving by or the ocean coming onto the beach. I also like the colors that are revealed from the lights in the area.
Hi, I'm Howie
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Search results
The 5th Spot
Al Pacino narrates some Sea Otter 2008 downhill action. ...
Posted April 28, 2008 in North America
2016 Sea Otter Classic early bird camping reservations open Monday
be made on the Sea Otter Classic website camping page . The full 2016 Sea Otter Classic website will go live on Nov. 2 for athlete registration and other functions. The 2016 Sea Otter Classic ...
Posted June 5, 2015 in North America
BRAIN dishes on the first day of Sea Otter
in the eclectic ambiance that has made Sea Otter the industry's largest, most important annual consumer event. ...
Posted April 16, 2015 in Industry News
Participation surges for 2015 Sea Otter Classic
percent). Sea Otter has grown in size and scope beyond its cycling core, with more product categories on display, organizers said. To meet the increased demand, the Sea Otter Expo has been expanded. "For 25 ...
Posted March 3, 2015 in North America
Send BRAIN your Sea Otter product news
clothing and nutritionals. All products must be on display at Sea Otter. Companies should send product ...
Posted February 27, 2015 in North America
Sea Otter goes high tech with smartphone app
hits about Sea Otter, festival information and live race results. Attendees can tap on a booth ...
Posted March 19, 2015 in North America
Sea Otter Classic: Our final roundup of new products
New helmet brand Shred was at Sea Otter for the first time to show how it uses a proprietary hexagon ...
Posted April 20, 2015 in North America
Yuba and Currie team up on electric cargo bike to be launched at Sea Otter
PETALUMA, Calif. (BRAIN) — Yuba Bicycles and Currie Technologies have teamed up to launch the Spicy Curry, a electric cargo bike that will be officially introduced at next week's Sea Otter Classic. The companies will have a fleet of the new model, called the Spicy Curry, ...
Posted April 2, 2015 in Product/Tech
The 5th Spot
Click title to visit BRAIN's Facebook page to see pictures from Sea Otter. ...
Posted April 14, 2011 in North America
Sea Otter Classic
to Sea Otter to participate in some of the sport's most competitive and enduring events. Hundreds of pro cyclists, including national, world, and Olympic champions, attend Sea Otter to race and meet with fans. ...
Posted October 6, 2014


text:
Re: destination_rate_delay and connection_reuse_time_limit
Expand Messages
- Hi Viktor,Thanks for the help.I believe I've activated the next hop feature in my transport table.If I understood it right, all I had to do is tell postfix that these domains belongs to my named transport specifying the domain.So this is how it is now:criticaldomain.tld slow:criticaldomain.tlddomain.tld slow:criticaldomain.tldIs it right?Thanks once again.Att.--Rafael Azevedo | IAGENTEFone: 51 3086.0262MSN: raffus@...Visite: www.iagente.com.brEm 07/01/2013, às 14:47, Viktor Dukhovni <postfix-users@...> escreveu:
On Mon, Jan 07, 2013 at 02:37:03PM -0200, Rafael Azevedo - IAGENTE wrote:
I've done something very similar.
If you want help, please take some time to read and follow the
advice you receive completely and accurately. "Similar" is another
way of saying "incorrect".
I created different named transports for specific domains and
have all domains I need a special treatment to use this named
To achieve a total concurrency limit across multiple destination
domains, you must specify a common nexthop, not just a common
So since I'm using Postfix + MySQL, I have a transport table with
all domains and destination transport. Its quite the same thing
you're proposing.
No, it is not, since it leaves out the common nexthop which
consolidates the queues for all the domains.
Yet, I'm still with the same problem.
Do take the time to follow advice completely and accurately.
So in the real life, I have about 10.000 domains that are hosted in
the same hosting company. This company has a rigid control of their
Your best bet is to get whitelisted by the receiving system for a higher
throughput limit.
If your average input message rate for these domains falls below the
current cap, and you're just trying to smooth out the spikes, the
advice I gate is correct, if you're willing to listen.
Is there anything else I can do to have a better control of my throughput?
Understand that Postfix queues are per transport/nexthop, not merely
per transport. To schedule mail via a specific provider as a single
stream (queue), specify an explicit nexthop for all domains that
transit that provider. Since you're already using an explicit
transport, it is easy to append the appropriate nexthop.
Any help would be very appreciated.
Ideally, you will not dismiss help when it is given.
- Rafael Azevedo - IAGENTE:
> > When all greetings fail with 4xx or whatever then Postfix willNo it doesn't. Postfix logs "delivery temporarily suspended" and
> > suspend deliveries.
> I have no idea about what I'm doing wrong, this really doesn't
> happen in my servers.
skips Yahoo until the "dead host" timer expires.
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text:
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Chaz Mang, from left, Victoria Kissinger and Victoria Jones share a hammock at the Austin City Limits Music Festival.
Jack Plunkett/Invision/AP
October 9, 2015 |
Fresh 102.7 Fall Fest at the Theater at Madison Square Garden in New York.
Greg Allen/ Invision/AP
October 8, 2015 |
If we have information that is incorrect on this itinerary, please
send us an email
© Copyright 2015 Pollstar. All Rights Reserved.
Use of information on this website is subject to
License Agreement.
Tickets for dates listed may not yet be on sale. Dates may change without notice.


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Vivid Seats can hook you up with the best Obie Trice tickets. Nothing is ever sold out as Vividseats.com is the spot for tickets to every show on the Obie Trice tour. Whatever seats you are looking for, we have tickets to all Obie Trice tour dates. All available events with Obie Trice tickets are listed above. Our website is completely secure and we guarantee your privacy when buying Obie Trice concerts tickets.
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text:
"I can resist anything except temptation."
-Oscar Wilde, "Lady Windermere's Fan"
Of the myriad things wrong with politics in America today, perhaps the most insidious is that too many of our representatives view elected office as a career path rather than a public service. Our Founders never intended for political careerists to run the country. They knew the corrupting influence of political power, and luckily for the rest of us, they possessed the strength of character to resist it.
If only we had more men like Washington and Jefferson in office today. Instead, we have a veritable pantheon of self-seeking, self-interested egotists unable to resist the siren song of corruption. A glaring example of this pervasive problem may be found in the Old Dominion. Virginia governor Bob McDonnell is under fire for playing the oldest game in the book: accepting gifts in exchange for political access and favors. Slate's Dahlia Lithwick profiled the scandal in her recent article, "Virginia is Corrupt."
"Embattled Gov. Bob McDonnell has probably just cratered a once-promising political career over $145,000 in undisclosed gifts – each worthy of its own episode of Real Housewives of Richmond – including a $6,500 Rolex, a New York shopping spree for his wife, limo rides, catering for his daughter's wedding, and a ride in a Ferrari. Is it shocking that McDonnell and his wife twisted themselves into pretzels to shill for the donor company's weird tobacco-based nutritional supplements?"
Undoubtedly these revelations come as a great disappointment to many McDonnell supporters in Virginia and around the country. Not long ago, McDonnell was a "Golden Boy" of the GOP. So much about him bespoke integrity and earnestness, principle and trustworthiness. Talk of presidential potential circulated widely. Now, he and his family's shameless abuse of the Governor's position have made him radioactive and his poll numbers have plummeted.
Democrats Remain Silent as Obama Economy Kills Jobs, Freezes Wages Amid More Layoffs to Come | Donald Lambro
For it before she was against it: Hillarybot flip-flops on TPP after praising it repeatedly until recently | Allahpundit


text:
Another year, another Coachella in the books! Although, I am a little sad that I'll be missing out on Stagecoach, as it's the most fun and easiest (work-wise) of the festivals. I'm really glad to be home, but it is short-lived, as I'm leaving tomorrow for a wedding in Miami! I've never been to Florida before so I'm a little excited; plus, I get to hang out with some awesome people and celebrate love!
I must mention that I put together some fantastic recipes for you guys before I left for Indio, but I didn't end up having any spare time (seriously, none) to post them, so I'm finally getting around to it! But, before we get to the pizookie, I wanted to share some photos from my 3 weeks in the desert.
It was an interesting time to say the least. Dust storms, tackling a thief (that was weird!), dealing with many set-backs, spending time with some great friends and of course, karaoke! I've missed my kitchen, bed, shower, dogs and family/friends, maybe the blogging bit, too. 😉
Without further ado, I bring you a Spring-inspired, Lemon Raspberry Pizookie! I took a shortcut and topped it with an Almond-based Vanilla Ice Cream, but you can definitely make your own. As much as I love the traditional chocolate chip pizookies, this version is insanely good, and not TOO sweet. I can't wait to try out some different variations of this in the future.
One Year Ago: Nuts & Seeds in Raw Food Desserts
Two Years Ago: Homemade Strawberry BBQ Sauce
- ¾ C. + 1 T. Unbleached All-Purpose Flour
- ⅓ C. Organic Sugar
- ⅓ tsp. Baking Soda
- Pinch of Sea Salt
- ¼ C. Coconut Oil, Melted
- 1 tsp. Ground Flaxseed
- 3 T. Non-Dairy Milk
- 1 tsp. Lemon Juice
- ½ tsp. Lemon Zest + Extra for Garnish
- ¾ tsp. Vanilla Extract
- ⅓ C. Fresh Raspberries + Extra for Topping
- 2-3 Scoops Vegan Vanilla Ice Cream
- Preheat oven to 350F.
- Sift the flour, sugar, baking soda and salt together in a mixing bowl.
- Whisk the coconut oil, flaxseed, non-dairy milk, lemon juice, lemon zest and vanilla extract together in a small bowl with a spout.
- Add the wet ingredients to the dry and stir together until evenly combined, with no dry pockets. Spread the mixture out in a 8-9" pie pan or cast iron pan.
- Gently press the raspberries into the top of the dough and bake for 15-18 minutes, or until the top is golden.
- Take out of the oven and let cool for 3-5 minutes before topping with ice cream, lemon zest, and raspberries. Serve immediately!


text:
Rosetta Resources Inc. is entering the Permian basin with plans to buy assets from Comstock Resources for $768 million, subject to customary closing adjustments.
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text:
The timeless Nike Air Max 1 brings us back to '92 Barcelona in it's US Olympic inspired colorway. Go for Gold at DVSN WEST.
air max 1
Nike Air Max 1 White/Gum
Nike Air Max 1 "Vapor Green"
Nike February Delivery
Fresh new styles from Nike have hit the shelves at DVSN WEST, available in Mens US 8-13.
The iconic visible air unit makes it's way to the Air Max Tavas, offered in a combo of lightweight mesh and suede in monochromatic reds and blacks. Last but not least is the always essential Air Max 1 in a bold Daring Red and Neutral Grey Mist outfitted in suede and nylon mesh with seafoam green highlights.
For purchasing details, give us a call at 303.800.4448
Photos courtesy of @june_yur
Nike "Space Blue" Pack
The 'Space Blue' Pack is, of course, named for the hue is uses but what really stands out is the floral print along the upper. It's unusual to see a floral print hit drop in the fall but if anything it only serves as a reminder that blue skies and sunny days are just a plane ride away. Call 303.800.4448 for purchase details.
***Air max 1 releases 11/18***Rosherun releases 11/21***
Nike Air Max 1 Premium Pack
Junior's Top 50 Shoes of 2013
It may seem late, but I had to let the year end before I could put together my top 50 list. What started out as a list of over 100 shoes is now cut down to my favorite 50 of the year. Enjoy!
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Deviant Art
Shadow!ItalyxReader Part 1REMINDER: I DON'T OWN DREAMTALIA OR SHADOW!ITALY!! You sillies should know that by now~ Anyway, enjoy!Shadow!ItalyxReader Part 12 years ago in General Fiction More Like This
It was a normal night in your small hometown of ((name of hometown)). You were sitting at home, which was a small apartment with one bedroom, a bathroom and a living room that was connected to the kitchen. Comfy on your couch, you turned the TV off and snuggled into your blanket more as you closed your eyes and soon fell asleep.
You opened your eyes to see you were sitting under a tree. It was sunny and warm, looking down you saw small flowers of various colors surrounding you as they growing in the green grass. You smiled, slowly standing up as you began to walk out into the field ahead of you. You look up, rays of sunlight hitting your face softly.
"This feels so real…" you said as you smiled softly.
"But it is real." A voice said.
You turned around to see no one there. "But there was a voice." you said, turning back around. As you did, you
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The evergreen foliage is glossy, and makes an elegant addition to borders, herb gardens or patio containers. Each spring, Bay trees are smothered with clusters of pale yellow flowers which are highly attractive to bees. Laurus nobilis also holds an RHS Award of Garden Merit. Height: up to 12m (40'). Spread: 10m (30').More info
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The final look at captured gameplay from SEGA Rally, caught lovingly on an Xbox 360 by cameraman James. His name is James, you know. Ask him about Beefy.
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The beginner's guide to Prison Architect How to prepare your very first prison.
Destiny: The Taken King guide Light level 290! PVP! Raiding!
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The influence of emotional target cues on prospective memory performance in depression
ABSTRACT This study investigated the impact of emotional valence on event-based prospective memory performance in depression. Thirty individuals with depression and 29 healthy adults performed a prospective memory task in which the emotional valence of the prospective targets was manipulated (positive, neutral, negative). Collapsed across all valence conditions, healthy adults outperformed individuals with depression in the prospective memory task. This effect was qualified by planned contrasts indicating that the two groups only differed when responding to positively valenced cues, reflecting a positivity effect in healthy adults. These data are in line with previous research, which shows that healthy participants better remember positively valenced cues, but are the first to show an absence of this effect in those with depression.
Full-textDOI: · Available from: Matthias Kliegel, Sep 27, 2015
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Article: The influence of emotional target cues on prospective memory performance in depression
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- SourceAvailable from: Michael Weinborn
- "SD = 1.84). The HDS group's mean BDI-II score was similar to or higher than those reported for depressed or HDS groups in previous PM studies (Altgassen et al., 2009, 2011; Chen et al., 2013; Li et al., 2013; Rude et al., 1999). Three participants (all in the HDS group) were on anti-depressant medication . "
Article: Cognitive control processes underlying time-based prospective memory impairment in individuals with high depressive symptomatology[Show abstract] [Hide abstract]
ABSTRACT: The current study compared time-based prospective memory (PM) for individuals with high depressive symptomatology (HDS) and low depressive symptomatology (LDS). We examined PM accuracy rate, clock-checking frequency, and decrements in ongoing task performance (i.e., costs to ongoing tasks) associated with an embedded time-based PM task. HDS participants demonstrated numerically lower but statistically comparable clock-checking frequency to LDS participants. However, their PM performance was significantly poorer than that of LDS participants. The pattern of observed costs to ongoing tasks and correlational analyses between ongoing task performance and PM accuracy showed that, relative to LDS participants, HDS participants were restricted in their allocation of attentional resources to support PM. We concluded that although HDS and LDS participants externally controlled their time-based PM task performance (i.e., clock-checking) similarly, the HDS participants lacked the cognitive initiative to allocate attentional resources to internally control PM task performance. Such internal control might reflect time-estimation processes, the resources required to maintain the PM task response intention, and/or the ability to coordinate the PM task response with ongoing task demands. To our knowledge, this is the first paper to have examined time-based PM strategies used by HDS individuals beyond clock-checking. The data suggest that interventions that encourage intermittent strategic reviews of PM goals may be beneficial for individuals with high depressive symptomatology.Acta psychologica 06/2014; 149:18–23. DOI:10.1016/j.actpsy.2014.02.010 · 2.19 Impact Factor
- "Furthermore, consistent with the predictions of both relevant theoretical accounts, we found greater depression effects for time-based compared to event-based PM. The null group effect for event-based tasks is consistent with two previous studies that found no depression-related event-based PM deficits (Albin´ski et al., 2012; Altgassen et al., 2011). However depression-related deficits have been demonstrated when event-based PM targets were non-focal to ongoing tasks, and thus required more attentional resources to detect (Altgassen et al., 2009). "
Article: Patterns of Prospective Memory Impairment Among Individuals with Depression: The Influence of Cue Type and Delay Interval[Show abstract] [Hide abstract]
ABSTRACT: The present study investigated the impact of cue type and delay interval on prospective memory performance in depressed, compared to non-depressed, individuals using a clinically relevant measure, the Memory for Intentions Screening Test. The depressed group demonstrated impaired performance on time-based, but not event-based, prospective memory tasks relative to the nondepressed group. The depressed group also demonstrated impaired prospective memory on tasks with longer delay intervals (15 min), but not on tasks with shorter delay intervals (2 min). These data support theoretical frameworks that posit that depression is associated with deficits in cognitive initiative (i.e., reduced ability to voluntarily direct attention to relevant tasks) and thus that depressed individuals are susceptible to poor performance on strategically demanding tasks. The results also raise multiple avenues for developing interventions (e.g., implementation intentions) to improve prospective memory performance among individuals with depression, with potential implications for medication and other treatment adherence. (JINS, 2013, 19, 1-5).Journal of the International Neuropsychological Society 03/2013; 19(6):1-5. DOI:10.1017/S1355617713000180 · 2.96 Impact Factor
- "Furthermore, our results showed that high scores on the Depressive dimension impair PM performance, both in terms of accuracy and latency in the global condition, whereas high scores on the Obsessive–Compulsive scale impair PM accuracy in the local condition. These results corroborate previous findings, which demonstrated that depressive emotional states (Altgassen et al., 2009; 2011; Rude et al., 1999), and obsessive–compulsive tendencies (Cuttler & Graf, 2009; Marsh et al., 2009) lead to a failure to perform the intended action. "
Article: The role of visual perceptual style and personality disorder traits in event-based prospective memory[Show abstract] [Hide abstract]
ABSTRACT: The aim of this study was to investigate the role of global/local processing style, field-(in)dependence, and personality disorder traits in event-based prospective memory performance. One hundred and fifty participants took part in an experiment, where they were administered a computerized version of Navon's global–local task. The PM task required participants to press a designated key whenever a blue compound stimulus was presented. Participants were then administered measures of field-(in)dependence and personality disorder traits. Data were submitted to logistic regression and hierarchical regression, separately for the two conditions (global/local). Results indicated that with respect to condition, global/local processing style, field-(in)dependence, and specific personality disorder traits differently affect PM performance.Personality and Individual Differences 11/2012; 53(7):912–916. DOI:10.1016/j.paid.2012.07.002 · 1.86 Impact Factor


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Marcus Niebuhr Tod
4 of 4 portraits of Marcus Niebuhr Tod
Marcus Niebuhr Tod
by Walter Stoneman
bromide print, 1947
5 1/2 in. x 4 in. (140 mm x 103 mm) image size
Commissioned, 1947
Photographs Collection
NPG x185704
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- Marcus Niebuhr Tod (1878-1974), Classical scholar and Fellow of Oriel College, Oxford. Sitter in 4 portraits.
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- Walter Stoneman (1876-1958), Photographer. Artist associated with 18496 portraits, Sitter in 8 portraits.
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Rapid detection devices for pathogen vectors are case study in leveraging small business innovation funding By Maj. Vanessa R. Melanson When military forces arrive in a new operational area, military preventive medicine personnel—preventive medicine specialists, entomologists and environmental science engineers—assess the environment, identify health threats and propose mitigations. Vector-borne diseases are one of the primary readiness threats, and the arthropods (insects and arachnids) that transmit pathogens to people account for about 60 percent of the military's priority pathogens list. Vector pathogen detection (VPD) provides military preventive medicine personnel the information necessary to implement specific vector-control measures and disease prevention countermeasures. VPD can minimize disease by sampling arthropods for […]
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your so called nobody....this is done for a reason...why? come in and see why.
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[quote:Anonymous Coward 28058392:MV8yMDY0NjgyXzM0Nzc3MjEzXzlGMkNFRjMz] [quote:mysterynomore:MV8yMDY0NjgyXzM0NzM3MzgzX0JBQUM5ODhE] [quote:Open Your Eyes:MV8yMDY0NjgyXzM0NzM3Mjg0XzI1MEE2NzE5] Tell us the world's biggest secret [/quote] There is no world secret. The energy lines were deactivated in the past...that's why were in this state. Everything is energy...to change things...it can only be done through that field. The whole mechanics of our world is imitated to go in a course directive..there is manipulation on every level of society. I can see that clearly..every person I come in contact with, I know them. That is there signature..frequency. It's a given that the earth will adopt it's full spectrum. The vein lines that run through it's system will not be hindered in our near future. [/quote] http://www.godlikeproductions.com/forum1/message2066889/pg1 Hi - link not my thread but I wrote some comments re Hunger Games inside. I spend a lot of energy worrying that this planet is Lost. I have been trying to think more positive lately but it isn't easy because the Badness seems to always win. And you're right, the Turnaround has to be an internal process. That's because the external environment is now so polluted with manipulations, the average human can no longer overcome this pervasive oppression. It's Spiritual Warfare, ultimately. I try not to despair that we will never get help. But each of us has to See what's wrong and then Pray for it to be corrected, and be Willing to make genuine changes. Our Father, Who art in heaven Hallowed be thy Name Thy Kingdom come Thy will be done On Earth As it is in Heaven [/quote]
Original Message
Before I start and explain things...I have no interest in replying to ignorant idiots.
I've done this for a reason...you'll find out the reason as we go along.
It will only go out on this site and this site only...I will not post it out beyond here.
This is a once only thread............................
I'm not here to convince people at all....I don't give a rats arse if i'm believed or not.
There is always a reason behind why I post things.
There are three like me on this planet....we stem from the old mystery schools...way before gnostic or other known mystic schools that inhabited our history.
I don't follow organized religion or god or gods.
I have no directive from any being except my own ability.
We are shamans...heirophants.
We guided intitations in the original mystery schools.
The first original site is the giza complex..(pyramids)
certain ptb were intitated in those schools that we guided.
That's why I know who they are and what they are..
I have crossed paths through the ages with that lot as I have in this life time. They know of me already.
They know not to cross a certain line.....
I never see myself as different to the whole of humanity..I don't see myself superior in any sense of the word.
Were all the same in connection.
It's not just in our hands to change things...there are many out there that will combine to this change.
The change won't happen through preaching knowledge or wisdom to crowds..it will be done inhouse behind closed doors.
We have no interest in going before the public domain.
The only difference between us is that we were intent in going to places through the grid lines or source as some might say....were others weren't prepared to do so.
There were dangers involved in holding certain energy lines.
Because we were commited in our chosen field...were able to not be as closed through certain incarnations..we hold that energy to some extent in our incarnations.
Were good at what we do..that's not being big headed... because those thoughts just rest there and don't surface in the conscious.
We know that larger picture and what it entails.
We come into these incarnations to activate those energy lines that existed on this planet in ancient times.
I wrote the majority of things in the primal grid thread...
There is one difference between us and others that have come along in the past....we will use agression to protect the sacred.
This change is going to happen...there is no one or anything that can stop it.
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|Publication number
|Publication type
|Application number
|Publication date
|Jun 22, 2004
|Filing date
|Aug 19, 2002
|Priority date
|Aug 17, 2001
|Fee status
|Publication number
|Michael Graft, Lev Nagli
|Original Assignee
|Florida Institute Of Phosphate Research
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (14), Referenced by (24), Classifications (4), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a Continuation-in-Part and claims priority to U.S. patent application Ser. No. 60/313,189 filed on Aug. 17, 2001.
1. Field of the Invention
This invention deals with the evaluation of mineral ores and the identification of components in the ores and the ability to selectively determine with a high degree of accuracy the content of such ores. In specific, by using the apparatus and method of the present invention, wanted or unwanted chemical species can be identified, thus making this an effective screening tool for rapid analysis of ores in mining applications. It is also anticipated that the present invention may be deployed in any application for which the identity of a chemical species is sought.
2. Description of Related Art
The need for instantaneous evaluation of mineral contents on moving belt systems has led to the necessity of remote sensing techniques to instantly differentiate between corresponding minerals to select desired mineral ores from those that are undesirable. This selection may be based on selective influence of the different kinds of irradiation on those minerals, whereby discrete pebbles are analyzed within a fraction of a second for a characteristic that can distinguish between "accept" and "reject" fractions. At present when dealing with moving belt systems, mineral evaluation is mainly performed using photometric, radiometric, steady-state luminescence, gamma-ray or X-ray fluorescence, and neutron absorption characteristics are mainly used for mineral evaluation.
U.S. Pat. No. 4,365,153 to Siegel describes the detection of certain minerals, including zinc, tungsten, fluorine, molybdenum, mercury, and other metals using a photoluminescence method. The basis of selective detection is that the lifetimes of photoluminescent emissions of many industrial minerals are much longer than the lifetimes of photoluminescent emissions of background materials that are likely to occur at the Earth's surface. The measurement of the photoluminescent response measured here is based on a response-retention factor and not on a direct readout at the time of irradiation. The detection here is based on taking a delayed readout to identify the minerals of economic interest after enough time has elapsed to enable unwanted sources of photoluminescence to decay.
Broicher (U.S. Pat. No. 5,410,154) describes detection of quality alterations contained in goods as they progress on a moving belt. The use of laser-induced luminescence, reflected light, and temperatures including detection of signal intensity and the fading behavior of the signals in definite spectral ranges is disclosed. This approach was also used by AIS Sommer GmbH of Germany, in their laser-induced fluorescence (LIF) analyzer for quality control in minerals and mineral processing. The LIF analyzer includes two light detector systems with three photomultipliers each, which evaluate three spectral bands in two time windows each. Such a system was employed in the Kirumna phorphorus iron ore mine in Sweden.
The limitation of LIF analysis is that its accuracy depends on the complexity of the composition of the ore and the concentration and fluorescence properties of the critical minerals in relation to all the other minerals present.
Another approach to differentiation of samples is described by White (U.S. Pat. No. 4,423,814). Here the natural luminescence of the accept and reject fractions is similar. The basis of separation of magnesium-bearing ore particles is obtained by first conditioning the exposed magnesium-rich mineral with a surface coupling agent of hydroxquinoline, then irradiating the conditioned ore to excite and induce fluorescence and then effecting separation of the magnesium-rich minerals from the lean ore particles by detection of the difference of the intensity of the fluorescence. This method detects ores having high magnesium contents on the surfaces of the pebbles.
Many similar methods have been used in the past to screen samples based on physico-chemical properties. Another example of this is selective flotation of phosphates and dolomites. As stated above, the difficulties of selective flotation of phosphates with high magnesium content are explained by similar physico-chemical properties of phosphates and dolomites. This problem exists also with other ores, thus making it desirable within the mining field to find separation systems that can quickly distinguish between wanted and unwanted ore fractions.
Alexander (U.S. Pat. No. 5,847,825) describes a method and apparatus for detection and concentration measurement of trace metals using laser-induced breakdown spectroscopy (LIBS). LIBS is a simple, rapid, real-time analytical technique based on the analysis of the spectral emission from laser-induced sparks or plasma. Pulsed laser radiation is first focused to a small spot on the sample material. When power densities exceed hundreds of MW/cm2, a high-temperature, high-electron-density laser microplasma is formed. The temperature of this plasma initially is very hot: 104 to 107 □ C. At such a high temperature, any sample material is broken down, vaporized and ionized. As the plasma cools down to the point when neutral atoms in excited states are formed, the excited species relax and emit optical energy at characteristic wavelengths. The emission can then be spectrally resolved to identify the elemental species that are present in the sample based on the presence of the characteristic lines.
It has been shown that LIBS is practical in situations, which require very fast, real-time measurements with no sample preparation. One such method is a penetrometer system for subsurface spectral analyses; such a system being described in Theriaul et al. (U.S. Pat. No. 6,147,754). Here, elemental identification using a cone penetrometer unit is achieved by using atomic spectral analyses of contaminants that are stimulated by a laser-induced breakdown of the soil containments to be determined.
Potzchke (U.S. Pat. No. 5,042,947) describes a scrap detection system using another LIBS system. Here a method and apparatus is disclosed whereby metal particles are detected in the context of being contained in compositions of alloying metals. Sorting of metal particles is effected by a plasma process, which cleans and then identifies the particles of interest. However, these metal particles are not in ion form as are those contained in mineral samples.
It is therefore an object of the invention to provide a LIBS system that is capable of detection of trace metals in an ore sample, such metals even being in an ionic species form.
It is a further object of the invention to provide a low-cost multi-element analysis system adapted to being compact and requiring no sample preparation.
It is another object of the invention to provide a system for sorting mineral ore samples which allows for rapid sorting of minerals in a moving belt system.
The present invention comprises a system and a method for mineral sorting and detecting, including remote sensing, and more particularly, for real-time detection and content evaluation of minerals or trace concentrations of elements in materials as they are conveyed on a moving belt. The instant invention employs a laser-induced breakdown spectroscopy (LIBS) system wherein intensity ratios of the emission lines characteristic for specific elements or minerals enable detection of the same while on a moving belt. Because associated minerals have different chemical compositions, namely, major or minor elements, the relative intensities, defined by their characteristic spectral lines, enables all phases to be consistently identified and assessed within a short time that is consistent with both LIBS and the moving belt system.
The steps to the invention include establishing a spectral signature ratio for at least one predetermined substance, the signature having a first intensity at a first wavelength relative to a second intensity at a second wavelength, applying pulsed laser energy to the mineral sample whereby plasma is produced, obtaining the spectral intensity of the plasma at the first and second wavelengths, and calculating the ratio of the spectral intensity at the first wavelength by the spectral intensity at the second wavelength whereby the presence or absence of the substance may be resolved.
It should be noted that the present invention permits the mineral sample to be analyzed substantially in real-time while in transit, such as moving on a conveyor belt. In a preferred embodiment, the steps include providing a computational processor and providing a radiation detector adapted to obtain the spectral intensity of the plasma. A database of spectral signatures for at least one substance is provided along with an output means communicatively coupled to the processor. The radiation detector, processor, and database are all communicatively coupled together wherein the spectral intensity is obtained by the radiation detector and measured values for the first and second wavelengths are passed onto the processor which calculates and compares the ratio to the database of spectral signatures and communicates the results to the output means. In another embodiment of the invention, the step of obtaining of the spectral intensity of the plasma may be time-gated to provide further discrimination of the sample's plasma.
The present invention is not limited to minerals, but to any compound for which the identity is sought in rapid analytical fashion. For example, food products (i.e., ingestible matter) may be rapidly analyzed for compounds or elements of interest.
FIGS. 1A, 1B are examples of laser-induced time-resolved luminescence of dolomite and phosphate rock, respectively. Excitation by nitrogen laser at 337 nm; repetition rate 500 Hz, E=50 mJ, delay=10 μs, gate=500 μs, Δλlum=450-525 nm.
FIGS. 2A-2D are spectra of Florida dolomite (FIG. 2A, delay=0, gate−9 ms; FIG. 2B, delay=5 μs, gate=1 ms) and apatite (FIG. 2C, delay=0, gate=9 ms; FIG. 2D, delay=5 μs, gate=1 ms) at λ=337 nm excitation.
FIGS. 3A-3D are luminescence spectra of Florida dolomite (FIG. 3A, delay=50 ns, gate 9 ms; FIG. 3B, delay=500 ns, gate=1 ms) and apatite (FIG. 3C, delay=50 ns, gate=9 ms; FIG. 3D, delay=500 ns, gate=1 ms) under λ=355 nm excitation.
FIGS. 4A-4P are spectra of one set of fractions by under 355-nm excitation, identified as fraction +�.
FIGS. 5A-5D are excitation spectra of Dy3+ (10 ppm) in Florida phosphate (FIG. 5A, λexc=349 nm; FIG. 5B, λexc=351 nm, /482//500=1.75; FIG. 5C, λexc=352 nm; FIG. 5D, λexc=355 nm, /482//500=1.45).
FIGS. 6A-6D are excitation spectra of Dy3+ (2 ppm) in Florida phosphate (FIG. 6A, λexc=349 nm, /483//500=1.05; FIG. 6B, λexc=351 nm, /483// 500=1.2; FIG. 6C, λexc=352 nm, /483//500=1.25; FIG. 6D, λexc=355 nm, /483//500=1.03).
FIG. 7 is a schematic of the system of the instant invention.
FIG. 8 is a Dy3+ intensity spectrum.
FIGS. 9A-9D are LIBS spectra for various minerals found in ores (FIG. 9A, apatite; FIG. 9B, dolomite; FIG. 9C, calcite; FIG. 9D, quartz).
FIGS. 10A,B are LIBS spectra of Florida apatite (FIG. 10A) and dolomite (FIG. 10B).
FIGS. 11A-11D are time-resolved LIBS spectra of Florida apatite (FIG. 11A, delay=0, gate=9 ms, /606//518=2.7; FIG. 11C, delay=500 ns, gate=9 ms, /606//518=8.6) and dolomite (FIG. 11B, delay=0, gate=9 ms, /606//518=0.3; FIG. 11D, delay=0, gate=500 ns, /606//518=0.1).
FIGS. 12A-12D are spectra of time-resolved LIBS for wet apatite (FIG. 12A, delay=0, gate=9 ms, /606//519=4; FIG. 12C, delay=1 μs, gate=9 ms, /606//519=19) and dolomite (FIG. 12B, delay=0, gate=9 ms, /606//519=0.35; FIG. 12D, delay=0, gate=500 ns, /606//519=0.2).
FIGS. 13A-13J are LIBS spectra of various minerals that can be treated by the system and method of the present invention [FIG. 13A, corundum, Al2O3; FIG. 13B, danburite, CaB2(SiO4)2; FIG. 13C, fluorite, CaF2; FIG. 13D, galenite, PbS; FIG. 13E, hydrozinkite, Zn5(CO3)2(OH)6; FIG. 13F, magnesite, MgCO3; FIG. 13G, quartz, SiO2; FIG. 13H, willemite, Zn2SiO4; FIG. 131, wulfenite, PbMoO4; FIG. 13J, zircon, ZrSiO4].
FIG. 14 is a table showing Rare-Earth concentration in Florida Apatite determined by Inductivity Coupled Plasma Method (ICP).
FIG. 15 is a table showing I580/I530 distinguishing features in Apatite and Dolomite under 337 and 355 nm excitation.
FIG. 16 is a table showingDy3+ distinguishing features in Apatite and Dolomite under 337 and 355 nm excitation.
FIG. 17 is a table showing chemical analyses of the products received by LIBS.
FIG. 18 is a table showing LIBS data using PMP setup.
A detailed description of preferred embodiments of the present invention will now be presented with reference to FIGS. 1-13.
The instant invention includes an system and method for the identification of specific species in an ore sample. This is useful for the evaluation of phosphate with high dolomite content, but is not intended to be limited thereto, as the system and method also are applicable to other elements, ions, or compounds occurring in mined mineral ores. The detection of those ions is performed by a source of irradiation, such as a laser energy emitter or other suitable excitation source, and means for delivering to and focusing the irradiation, i.e., the laser energy emission, on a sample on a moving belt, or other conveyor means. The system further comprises a detection system and, in a preferred embodiment, a processor.
Selecting an ionic or elemental species in the desired fraction and performing a screening based upon an intensity ratio Iλ1/Iλ2, which is characteristic of the emission properties of the ion or elemental species contained in the sample, make positive detection of a desired sample. The detection is accomplished with the use of a LIBS system, or another applicable system commensurate with the parameters of the excitation and emission wavelengths deemed most suitable for the sample.
The laser source range of an illustrative embodiment encompasses, but is not intended to be limited to, ˜100-1000 Hz, with pulse energy of no less than 10 mJ. It is contemplated that the laser system may be selected based on subject ion or element, as being known to one of ordinary skill in the art. In addition to laser sources, a suitable excitation source may be employed after the subject wavelengths are determined; this excitation source being chosen based on the ion emission lines and the desired excitation wavelength desired.
Spectral analysis refers to a determination of the intensity of light as a function of wavelength. Any means of spectral analysis known in the art may be used, again, the choice being dependent on the particular application. In a preferred embodiment of the present invention, it was found to be desirable to use a ⅛-mm imaging spectrograph and an intensified thermoelectric-cooled ICCD camera, which is capable of imaging up to 500 spectra/second.
In order to differentiate between wanted and unwanted ore samples, an intensity ratio, /λ1//λ2, threshold is determined, being representative of the composition of the ore contained in the subject deposit. A thorough study of the ores is first made, which includes obtaining a complete spectrum of the minerals from the sample, using the spectral range 200-900 nm with spectral resolution 1 nm. In some instances, it may be necessary to lower the resolution to 0.1 nm in order to resolve spectrally close lines. By using this spectrum rather than any form of database information, it is possible to obtain a spectral fingerprint of the ore and its components, with any interference problems caused by impurities represented by spectral shifts or line-definition problems.
In addition, comparative spectra are then obtained using different power levels and different excitation wavelengths for the laser source. In addition, studies of the decay times of the different lines are made for use with time-resolved spectroscopy. The /λ1//λ2 ratio is then established by selection of two lines characteristic of a "good" sample, which exhibits good definition without interference from other materials.
The presence of a sample fraction in the stream is determined by measurement of its specific emission line intensities. The relative content of selected fraction is determined by the ratio between the numbers of the emission pulses associated with the selected fraction to the total number of emission pulses. This ratio is determined by an investigation of the mineral species contained in the subject ore fractions, both the "good" (wanted) ores and the "bad" (unwanted) ores.
The ratio technique of the present invention is suitable for ore samples having particle sizes from micrometer to large boulder sizes. It is within the scope of the invention to provide a portable version of the system, which provides an effective means of analyzing mine facial or perform in situ examinations within the mining site itself. The system may be applied to moving systems of all varieties known in the art; these including, but not limited to, flow cells, slurry systems, flotation systems, and other moving bed systems known in the art. These also include mechanical movement as well as chemical movement means. Because the ratio of the emission lines is determined for the subject ores from a specific location, the presence of organic impurities, water, other flocculents, and slurry agents or impurities does not affect the results, since the ratio is made from emission lines selected for their spectral purity. Indeed, any line that exhibits such interference is not of interest for establishment of the intensity ratios of the present invention.
In a further embodiment, the spectral analysis data can be output to a computer with a display monitor, combined with an electronic card or having an algorithm that enables the laser beam to synchronize with the ICCD, to measure two emission signals from two different pixels simultaneously, to calculate their ratio, to identify accept or reject fractions according to the ratio, to demonstrate the place of corresponding mineral on the computer screen, and then calculate the subject fraction content of desired or undesired ions or elements.
With respect to phosphate rocks, the intensity ratio of the characteristic emission lines of Mg at 518 nm and F at 604 nm enables a detection of pebbles having high dolomite content. Because dolomite (Ca, Mg)(CO3)2 contains Mg and not F, and phosphate Ca5(PO4)3(F,O):Ca5(PO4)3CO3 contains F but only minimal Mg, /518//604 enables that both phases be consistently identifiable within the time available for examination by LIBS.
The analytical line of Mg at 518 nm is characterized by a decay time of approximately 200 ns. This makes for an optimal time-resolution spectrum with a narrow gate of 1 μs. Under such conditions the intensity of the relatively broad band in the range 600-630 nm connected with carbonate is substantially lower, and the ratio /518//606 is higher. The decay time of the F characteristic line at 606 nm of approximately 500 ns is longer than that for Mg, but it is still relatively strong with gate of 1 μs, and apatite is easily detected. Damp samples of apatite and dolomite from a moving belt have been checked, and essentially the same spectra are detected. Thus a delay time is not needed, and time-resolved spectroscopy with zero delay and a gate width of 1 ms may be accomplished using intensified thermoelectric-cooled ICCD cameras.
The system and method of the present invention are further characterized by the following example.
Example 1 Use of LIBS to Differentiate Florida Phosphate Ores
Natural apatite contains several characteristic luminescence centers that enable differentiation from dolomites (FIG. 1A). The most widespread characteristic luminescence center is uranyl (UO2)2+, with typical vibrational green-band luminescence under nitrogen laser excitation as shown in FIG. 1B. Under close inspection of Florida phosphate rock, this moiety was absent; FIGS. 2A-2D show the spectra derived by laser-induced luminescence of the apatite (FIGS. 2C,2D) and dolomite (FIGS. 2A,2B) from Florida mines.
In order to find a distinguishing or "fingerprint" characteristic ion for identifying dolomite and apatite, ICP-MS analysis of Florida phosphates was performed. It was found that apatite contained rare earth elements, and in the case of the Florida apatites, these were present in quantities suitable for laser-induced luminescence analysis. As seen in Table 1, the highest concentration and quantum efficiency is for Ce3+, but this ion has a luminescence in the UV-violet portion of the spectrum and also has a very short decay time, comparable with times for organic material. Thus its luminescence would not be clearly seen if the sample contained a great deal of background organic matter. From the other rare-earth ions detected, Dy3+ was the best candidate owing to its favorable combination of concentration, quantum efficiency, and spectral and temporal characteristics. According to the Dy3+ excitation spectrum, the third harmonic of a Nd-YAG laser at 355 nm was deemed the most suitable among the lasers commonly available at present. Narrow lines of Dy3+ with long decay times of 500-600 ms appear under 355-nm excitation in apatites, but they have never been detected in dolomite (see FIGS. 3A-3D), since dolomite comprises a very poor matrix for luminescence center formation, and because of the isomorphous substitution of Ca2+ in apatite being much easier for the trivalent rare-earth elements than the divalent Mg2+ found in dolomite. Thus the fingerprinting ion was determined for the present embodiment.
To further investigate the efficacy of the Dy3+ for positive differentiation of apatite from dolomite, more than 200 samples were randomly chosen from ore. Two selective features were chosen to study: characteristic lines of Dy3+ and intensity ratios at 580 and 530 nm (/580//530). Typical spectra obtained under 355-nm excitation are presented in FIGS. 4A-4P.
The >200 samples were classified and identified as follows: Fraction +� in. Twenty-two samples having sizes greater than � in. were randomly chosen from the light-colored part of the ore: 9 were identified by X-ray diffraction as apatite and 13 as dolomite. By laser-induced time-resolved luminescence (LITRL), 6 apatites clearly demonstrated Dy3+while this ion was never detected in dolomite. The parameters using /580//550 are substantially the same.
Thirteen samples were randomly chosen from the dark-colored part, and all were identified by X-ray diffraction (XRD) as apatite. Dy3+ appears only in 45%, while the intensity-ratio feature was not possible to check due to a lack of dark dolomite for comparison.
Twenty-nine samples having sizes greater than ⅜ in. were randomly chosen from the light-colored part: 15 were identified by XRD as apatite and 14 as dolomite. By LITRL, 6 apatites clearly demonstrated Dy3+, while none was again detected in the dolomite. The intensity-ratio distinguishing feature enabled 12 apatite pebbles to be identified (80%), but one dolomite (7%) was also determined to be apatite.
Twelve samples were randomly chosen from the dark-colored part: 10 were identified by XRD as apatite and 2 as dolomite. Dy3+ appeared only in 2 samples (20%), while the intensity-ratio distinguishing feature enabled identification of 8 apatite pebbles (80%) with complete rejection of dolomite.
Sixteen samples having sizes greater than 0.156 in. were randomly chosen from the light-colored part: 10 were identified by XRD as apatite and 6 as dolomite. By LITRL, 8 apatites (80%) clearly demonstrate Dy3+, while again none was detected in the dolomite.
Twelve samples were randomly chosen from the dark-colored part: 11 were identified by XRD as apatite and 1 as dolomite. Dy3+ appears in 9 samples (82%).
Thirty-one samples having sizes greater than 16 mesh (approx. 1 mm) were randomly chosen from the light-colored part: 25 were identified by XRD as apatite and 6 as dolomite. By LITRL, 20 apatites (80%) clearly demonstrated Dy3+, while again none was detected in the dolomite.
Twelve samples were randomly chosen for the dark-colored part, and all were identified by XRD as apatite. Dy3+ appeared in 9 samples (75%), but no dark dolomite was available for comparison in this fraction.
Twenty-three were randomly chosen from the light-colored part: 16 were identified by XRD as apatite and 7 as dolomite. By LITRL, 9 apatites (56%) clearly demonstrated Dy3+, while again none was detected in the dolomite. The intensity-ratio distinctive feature enabled the identification of 13 apatite pebbles (81%).
Twelve samples were randomly chosen from the dark-colored part, and all were identified by XRD as apatite. Dy3+ appeared in 9 samples (75%), with no available dark dolomite available for the ratio comparison.
Eighteen samples were randomly chosen for the light-colored part: 15 were identified by XRD as apatite and 3 as dolomite. By LITRL 11 apatites (73%) clearly demonstrated the presence of Dy3+, while again none was detected in the dolomite.
Twelve samples were randomly chosen from the dark-colored part: 11 were identified by XRD as apatite and 1 as dolomite. Dy3+ appeared in 9 samples (82%).
The results of these studies are tabulated in Table 2, the data of which indicate that the main object is the light-colored fraction, where the average dolomite content was 33%, while that in the +� fraction was nearly 60% and in the +⅜ fraction, more than 50%. The dark-colored fractions usually contained 1% dolomite.
In order to address the problem that Dy3+ luminescence intensity varies strongly from apatite to apatite, an optimal excitation band was chosen. It is well known that Dy3+ has very narrow excitation bands, this being confirmed by the fact that in the apatite it is strongly excited by 355-nm radiation, but absolutely not at 337 nm.
FIGS. 5A-5D are luminescence spectra under different excitations of Dy3+ for a sample of sedimentary apatite from Florida with relatively strong lines of Dy3+. The most important parameter for apatite and dolomite differentiation is the ratio of luminescence intensities at 482 and 500 nm (/482//500). The best result was achieved for excitation under 351 nm, which was 1.2 times stronger than for excitation under 355 nm. FIGS. 6A-6D present the same data for Florida sedimentary apatite with weak Dy3+ luminescence lines. Because under 355-nm excitation the /482//500 ratio is very close to 1, it could be mistaken for dolomite, but under 351-nm excitation this ratio is 1.2 times stronger, and the identification is then correct. In addition, 351 nm exactly corresponds to the emission wavelength of excimer XeF lasers. Using a state-of-the-art laser, which has repetition rates up to 500 Hz with maximum energy of 20 mJ per pulse, further study of these energy parameters showed that Florida apatite having strong Dy3+ luminescence was detected with a pulse energy of 5 mJ or less. In the case of weak Dy3+ luminescence, the lowest level was determined to be 8-10 mJ.
In an additional embodiment, the sensitivity was improved by computerized spectral analysis using smoothing, which achieves an improvement of the signal-to-noise ratio by mathematical processing of the raw data. A widely used method of spectral data smoothing in the art is the moving window and polynomial curve fitting (the Savitzky-Golay method). This method also includes simultaneous processing of the data to locate peaks by the calculation of the spectrum derivatives. The moving window scans spanning M data points, moves along the data, and creates an estimation of smoothing spectrum or its derivative in the inner window point.
In order to computerize the analysis of spectral data, a software program was written containing the following elements:
1. Reading of the ASCII files
2. Smoothing by the Savitzky-Golay method (SGM)
3. Calculation of the first and second derivatives of spectrum data by SGM
4. Calculation of background by the least-squares method
5. Peak searching
6. Calculation of the peak amplitude above the background
7. Storing the results in Microsoft Excel files
The significant difference between apatite and dolomite is the presence of a peak near 483 nm in the apatite spectrum that is not present in the dolomite spectrum.
The purpose of the first step of the analysis is smoothing of spectra and checking for a peak in the 483-nm area. A 5-point SGM has been used for smoothing, which gives effective results for increasing the signal-to-noise ratio. It was determined that all apatite spectra have peaks in the 483-nm region (the average wavelength of the peak maximum is 483.250 nm, with a standard deviation of 1.572 nm). At that time only 7 of the dolomite spectra demonstrated a peak in this area (average wavelength 483.219 nm, standard deviation 2.144 nm).
Background calculation was made by the least-squares method. The parabolic approximation of the background gave satisfactory results, and the peak amplitude over the background was calculated for all spectra. This analysis showed that peak amplitude above the background for the apatite spectra is much higher than for the dolomite spectra. For apatites, the average value is 9.74%, with a standard deviation of 6%, while for dolomites the average value is 0.91%, with a standard deviation of 2.21%.
The system 10 of the instant invention is illustrated schematically in FIG. 7. This system 10 comprises a computer such as a PC 30 in circuit communication with a laser source 20, here a Nd:YAG laser. As described previously, other suitable lasers or non-laser excitation sources may be used, depending on the material to be analyzed and on the wavelengths sought for optimal resolution. The beam emitted from the laser 20 passes through harmonic crystals 21 and a filter 22 before passing through lens 25 and then impinging on the sample 23. The crystals 21, filter 22, and lens 25 serve to attenuate the laser beam, and thus the excitation energy passed onto the sample 23 is optimized. A suitable detection apparatus such as a CCD time-gated system may be used or a detection system based on photomultipliers may also substituted. Such a system is shown in FIG. 7 and comprises a semitransparent mirror 26 and interference filters 24 connected to photomultiplier tubes 26, powered by power suppliers 27. The signals generated by the photomultiplier tubes 26 are then transmitted gating and integrating electronics 28, which then sends the signal back to the PC 30.
In a further study of Florida apatite and dolomite, a light pulse of the 3 d harmonic of a Nd:YAG laser (355 nm, 30 ns) was used for luminescence excitation. The luminescent light after passing through the monochromator assembly comprising the crystals 21, filter 22, and lens 25 after contacting the sample 23 was transmitted to photomultiplier tubes (PMT) 26 via interference filters 24. The registered pulses were then transmitted to a memory oscilloscope, depicted as the gating and integrating device 28. Luminescence pulses at 480 nm consist of two elements: an intense fast element and a much weaker slow component, the fast component being approximately three orders higher in magnitude than the slow component. The decay time of the fast component is about 30 ns, and that of the slow component about 800 μs. At 500 nm only a fast luminescence component was detected, as shown in FIG. 8. The spectrum was recorded using an oscilloscope, and the amplitude of the signal was measured at a time delay of 500 ms. The spectrum and decay time of the slow component confirmed that this was due to the presence of the Dy3+ in the sample, identifying it as apatite. The luminescence spectrum of the fast component was approximately the same for apatite and for dolomite, this being attributed to adsorbed water and organic matter.
Further modifications of the apparatus 10 are also intended to be within the scope of the present invention. In the embodiment above, apatite sorting was based on comparative time-delayed measurement of the luminescence intensity at certain spectral points, namely 480 and 520 nm. In this embodiment, in order to detect the Dy3+ signal, which was very weak with respect to the background signal, a longer decay time was used, this being effected by the photomultiplier tubes" being started with a time delay. The PMT output delay was electronically regulated by the electronics 28, with both delay time and gate width being regulated. This enabled the weaker Dy3+ lines to be read as if they were strong; thus the time delay overcame the lack of intensity, and differentiation between dolomite and apatite was successfully accomplished.
To overcome another problem caused by the time-delay system, another approach to the gating aspect was employed. Owing to the large resistance of the output PMT, the "tail" from the fast non-characteristic luminescence component still hid the weaker Dy3+ luminescence, with a resulting sensitivity reduction. As an alternative approach, two PMT gated systems (Electron Tubes Ltd.) were used. The gating was based on switching out the PMT high voltage at a PMT cathode for time needed for delay (i.e., the gating time). The PMT housing, filter holder, and double PMT power supplier were also modified; these included coupled fiber connectors that enabled fibers to be used for simultaneously detecting two luminescence intensities at the two different wavelengths, 480 and 520 nm. The above substitutions and modifications are considered within the scope of ordinary skill in the art.
A further embodiment utilizes LIBS. FIGS. 9A-9D and 10A,B are comparison spectra of apatite (FIGS. 9A, 10A), dolomite (FIGS. 9B, 10B), calcite (FIG. 9C), and quartz (FIG. 9D). It may be clearly seen that the line at 604 nm, which is associated with F, belongs only to apatite, while the line at 518 nm, which is associated with Mg, belongs only to dolomite. Thus by using the ratio of the 604- and 518-nm lines (/604//518), confident dolomite versus apatite detection can be made using plasma-induced time-released luminescence spectroscopy (PITRLS). It was found that the signals were very strong with the laser pulse at 5 mJ, and detection was made without delay and gating.
Example 2 Use of LIBS for Apatite and Dolomite Differentiation
The dual PMT system was used to inspect 160 pebbles obtained from a Florida source. These were analyzed in a condition similar to a moving-belt system, namely, from a distance of 1 meter using only one laser pulse. Three groupings were made, and each of these was separated into "bad" as containing dolomite and "good" as being apatite. In addition, an outside laboratory to determine the constituents performed a separate chemical analysis. Those results are contained in Table 3, which illustrates that the "bad" fraction contained mainly dolomite with the mean /(MgO)//(P2O5)=0.7, while the "good" fraction is mainly apatite with the mean /(MgO)//(P2O5)=0.015, clearly 50 times lower.
The identification can also be enhanced by use of time-resolved spectroscopy. As shown in FIGS. 11A-11D, the analytical line of Mg at 518 nm is characterized by a very short decay time of 200 ns. By using a narrow gate of 1 μs, this may be further enhanced. Under these conditions the intensity of the relatively broad band in the range 600-630 nm associated with carbonate is substantially lower, and the ratio /518//606 is higher. The decay time of the F characteristic line at 606 nm of approximately 500 ns is longer than that for Mg, but it is still relatively strong with the gate of 1 μs, thus making apatite easily detectable.
One potential problem with analysis of raw ore samples is interference due to water in the material. FIGS. 12A-12D are illustrative spectra of wet samples. A comparison of these with the dry samples of FIGS. 11A-11D clearly shows no interference due to the presence of water.
The description above should not be considered as limiting the scope of the invention, but as merely providing illustration of some of the preferred embodiments of the instant invention. In light of the above description and examples, various other modifications and variations will now become apparent to those of ordinary skill in the art and are therefore considered within the scope of the invention without departing from the spirit and scope of the invention.
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|U.S. Classification
|International Classification
|Cooperative Classification
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|Oct 30, 2002
Owner name: FLORIDA INSTITUTE OF PHOSPHATE RESEARCH, FLORIDA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GAFT, MICHAEL;NAGLI, LEV;REEL/FRAME:013206/0454
Effective date: 20021027
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